The utility of the template effect in metal-organic frameworks

Guo, Xiuxiu; Geng, Shubo; Zhuo, Mingjing; Chen, Yao; Zaworotko, Michael J.; Cheng, Peng; Zhang, Zhenjie

doi:10.1016/j.ccr.2019.04.003

Cited by 82 publications

(43 citation statements)

References 161 publications

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“…Porous coordination networks (PCNs), 23,24 which comprise metal-organic frameworks (MOFs), porous coordination polymers (PCPs), 25,26 and hybrid ultramicroporous materials (HUMs), [27][28][29] exploit the modularity of their building blocks (metal ions/clusters, organic/inorganic linkers) to control topology, pore size, and pore chemistry in a manner that is infeasible for existing classes of materials. 30,31 PCNs can be readily assembled using crystal engineering principles [32][33][34][35][36] including the nodeand-linker, 37,38 molecular building block (MBB), [34][35][36]39 and supramolecular building block approaches. 40,41 Precise control over pore structure can be exerted by adjustment of the lengths, geometry, and functionality of the MBBs.…”

Section: Introductionmentioning

confidence: 99%

Crystal engineering of porous coordination networks for C3 hydrocarbon separation

et al. 2020

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C3 hydrocarbons (HCs), especially propylene and propane, are high-volume products of the chemical industry as they are utilized for the production of fuels, polymers, and chemical commodities. Demand for C3 HCs as chemical building blocks is increasing but obtaining them in sufficient purity (>99.95%) for polymer and chemical processes requires economically and energetically costly methods such as cryogenic distillation. Adsorptive separations using porous coordination networks (PCNs) could offer an energy-efficient alternative to current technologies for C3 HC purification because of the lower energy footprint of sorbent separations for recycling versus alternatives such as distillation, solvent extraction, and chemical transformation. In this review, we address how the structural modularity of porous PCNs makes them amenable to crystal engineering that in turn enables control over pore size, shape, and chemistry. We detail how control over pore structure has enabled PCN sorbents to offer benchmark performance for C3 separations thanks to several distinct mechanisms, each of which is highlighted. We also discuss the major challenges and opportunities that remain to be addressed before the commercial development of PCNs as advanced sorbents for C3 separation becomes viable.

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Section: Introductionmentioning

confidence: 99%

Crystal engineering of porous coordination networks for C3 hydrocarbon separation

et al. 2020

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“…MOFs are coordination polymers based on metal nodes and multitopic organic linkers, exhibiting impressive specific surface areas [23,24]. Crystalline MOFs are characterized by their uniformly structured nanoscale cavities and pore topologies, high adsorption affinity, and chemical tunability [25] for the pore environment and the outersurface [26,27].…”

Section: Introductionmentioning

confidence: 99%

Solid-phase microextraction coatings based on the metal-organic framework ZIF-8: Ensuring stable and reusable fibers

Rocío‐Bautista

Gutiérrez‐Serpa

Cruz

et al. 2020

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Chemical vapor deposition of MOFs (MOF-CVD) has been used to coat solid-phase microextraction (SPME) fibers with ZIF-8, by exposing ZnO layers to the linker vapor (2-methylimidazole). This ZIF-8 coating has been used as a seed layer in a following solvothermal MOF growth step in order to increase the ZIF-8 thickness. The combined MOF-CVD and solvothermal growth of ZIF-8 on the fibers result in a thickness of ~3 μm, with adequate thermal stability, and mechanical integrity when tested with methanol and acetonitrile ultrasonic treatments. The fibers have been evaluated in direct immersion mode using gas chromatography and flame ionization detection (GC-FID), for a group of target analytes including three polycyclic aromatic hydrocarbons (PAHs) and five personal care products (PCPs). The optimized conditions of the SPME-GC-FID methods include low amount of aqueous sample (5 mL), stirring for 45 min at 35 °C, and desorption at 280 °C for 5 min. The method presents limits of detection down to 0.6 μg L −1 ; intra-day, inter-day and inter-batch relative standard deviation values lower than 16%, 19%, and 23%, respectively; and a lifetime higher than 70 cycles.

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“…To tackle the problem of framework topological control and synthetic reproducibility in ZIFs, it seems reasonable to turn to templation, an approach often used in zeolite synthesis, and one that is gaining traction in the MOF community [26]. Unfortunately, unlike the negatively charged zeolite frameworks which can be templated by judicious choice of counter cations, most ZIFs are uncharged frameworks and therefore do not include counterions.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Scope of Macrocyclic “Shoe-last” Templates in the Mechanochemical Synthesis of RHO Topology Zeolitic Imidazolate Frameworks (ZIFs)

et al. 2020

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The macrocyclic cavitand MeMeCH2 is used as a template for the mechanochemical synthesis of 0.2MeMeCH2@RHO-Zn16(Cl2Im)32 (0.2MeMeCH2@ZIF-71) and RHO-ZnBIm2 (ZIF-11) zeolitic imidazolate frameworks (ZIFs). It is shown that MeMeCH2 significantly accelerates the mechanochemical synthesis, providing high porosity products (BET surface areas of 1140 m2/g and 869 m2/g, respectively). Templation of RHO-topology ZIF frameworks constructed of linkers larger than benzimidazole (HBIm) was unsuccessful. It is also shown that cavitands other than MeMeCH2—namely MeHCH2, MeiBuCH2, HPhCH2, MePhCH2, BrPhCH2, BrC5CH2—can serve as effective templates for the synthesis of x(cavitand)@RHO-ZnIm2 products. The limitations on cavitand size and shape are explored in terms of their effectiveness as templates.

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The utility of the template effect in metal-organic frameworks

Cited by 82 publications

References 161 publications

Crystal engineering of porous coordination networks for C3 hydrocarbon separation

Crystal engineering of porous coordination networks for C3 hydrocarbon separation

Solid-phase microextraction coatings based on the metal-organic framework ZIF-8: Ensuring stable and reusable fibers

Exploring the Scope of Macrocyclic “Shoe-last” Templates in the Mechanochemical Synthesis of RHO Topology Zeolitic Imidazolate Frameworks (ZIFs)

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